CN102666766B - Primer compositions to toughen adhesive bonds - Google Patents

Primer compositions to toughen adhesive bonds Download PDF

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Publication number
CN102666766B
CN102666766B CN201080046484.3A CN201080046484A CN102666766B CN 102666766 B CN102666766 B CN 102666766B CN 201080046484 A CN201080046484 A CN 201080046484A CN 102666766 B CN102666766 B CN 102666766B
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primer composition
component
composition
connection section
end connection
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CN102666766A (en
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S·阿塔尔瓦拉
I·C·布罗德里克
P·S·帕特尔
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Henkel AG and Co KGaA
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Henkel Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/226—Presence of unspecified polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/003—Presence of (meth)acrylic polymer in the primer coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a primer composition including a toughening agent can be applied to a surface to be bonded using a separate curable adhesive composition. The primer composition toughens cured reaction products of the adhesive composition. In some embodiments the primer composition can also enhance reactivity of the curable adhesive composition.

Description

Make the bonding toughness reinforcing primer composition of tackiness agent
Technical field
The disclosure relates to can be coated in the lip-deep primer composition that comprises toughner component to be bonded.When using curable adhesive by surperficial when bonding to treated surface and another, it is toughness reinforcing that described primer composition makes between described surface, to form bonding curing reaction product.
Background technology
Anaerobism tackiness agent is in the time being exposed to air, to remain liquid, but when being limited to the acrylate mixture of hardening while existing without air between metallic surface.Anaerobism tackiness agent has multiple industrial application, comprises locking screw thread fastening piece, sealing thread pipe connections, keeps cylindrical machine parts, sealing porous metal founding and weld seam and glued construction and non-structural part.
Conventional anaerobism tackiness agent formulation comprises monomer as (methyl) acrylate; Polymerization starter is as organic hydroperoxide; Be used for the curing promotor of catalysis anaerobism as benzoic sulfimide or aromatic amine; And the stablizer that slows down premature setting is as quinhydrones.
Solidify anaerobism tackiness agent and can there is enough intensity to adhesive substrate.But for some application, cure adhesive lacks desirable toughness, and what solidified is firmly bonding but easily crisp.Having proposed all ingredients reduces fragility and improves the toughness of solidifying anaerobism binder composition.The toughness of these reagent evenly being sneaked into the product of curing reaction in anaerobism binder composition and to said composition provides desirable improvement.But there is the restriction of practicality and economy in the toughness reinforcing dosage that can mix anaerobism binder composition before affecting adversely as viscosity for the character at described composition.
(as stainless steel or galvanized steel) can not fast setting on the 'inertia' metallic surface of some types for the anaerobism binder composition of some types.But, if use primer composition to anticipate surface, can improve anaerobism tackiness agent lip-deep curing at inert metal.The primer composition of one type comprises activator component and solvent.Conventionally, described activator component can be one or more metal-salts, its accelerate subsequently apply curable adhesive composition solidify, for example described activator component can make tackiness agent more fast and more completely solidify.But the primer of these activator types is conventionally containing reactive component, and therefore bonding character is the result of the adhesive reaction product that solidified.Described activator is not gained in strength or toughness to bonding.
United States Patent (USP) 3,591,438 people such as () Toback have described a kind of primer activator composition, and it solidifies for the acrylate-based adhesives accelerating peroxide and cause or sealing agent.The condensation product that described primer activator composition comprises (a) aldehyde and primary amine or secondary amine and (b) comprise oxidable transition metal compound as reductibility activator.Also disclose this activator compound has been dispersed or dissolved in the volatile solvent that comprises hydrochloric ether, as trichloroethane or Trichloromonofluoromethane, or in paint type (lacquer-type) solvent, in acetone or ethyl acetate or aromatic hydrocarbon, as benzene or toluene.
United States Patent (USP) 5,811,473 (people such as Ramos) have described the curing primer activator composition for accelerating can anaerobism curing binder composition.Described primer activator composition comprises transistion metal compound activator; Have at least one hydrocarbon key, nonflammable, the poly-fluothane hydrocarbon of the liquid that do not destroy ozone and can form with poly-fluothane hydrocarbon the alkanol of azeotropic mixture.
The primer composition of another kind of type comprises curable monomer component, and can comprise metal activation agent.This primer composition and contact-type anaerobism tackiness agent interact and make this tackiness agent and solidify to form high-strength adhesive more fast and more completely.
Primer composition can improve substrate adherence, but it does not increase the bonding toughness of gained.In fact, the curing reaction product of primer monomer may form easy crisp layer or crisp pocket at whole adhesion area.
Expecting provides primer composition, improves the gained toughness of curing composition in the time that it is used together with tackiness agent.In some embodiments, expect also to provide the primer composition of the curing speed of accelerating can anaerobism curing binder composition.
Summary of the invention
Briefly, an embodiment discloses primer composition, and it comprises toughner component; And optionally comprise one or more in activator component, coactivator component, reactive component and carrier component.
Briefly, an embodiment discloses primer composition, and it comprises toughner component and reactive component; And optionally comprise one or more in activator component, coactivator component and carrier component.
Briefly, an embodiment discloses primer composition, and it comprises toughner component, reactive component, activator component; And optionally comprise one or more in coactivator component and carrier component.
Briefly, an embodiment discloses illiquidity primer composition, and it comprises toughner component, polymeric matrix, and optionally comprises one or more in reactive component, activator component, coactivator component and carrier component.
Described primer composition is coated on to the curing reaction product for the treatment of by curable adhesive composition to be bonded on the surface on another surface.Described primer composition can be before described curable adhesive composition, simultaneously or be coated in afterwards on adhesive surface.Described toughner component improves the toughness of the curing reaction product that forms bonding described curable compositions.In some embodiments, the curing speed of described curable binder composition can accelerate by described activator component.
Disclosed compound comprises any and whole isomer and steric isomer.In general, disclosed composition can be formulated as alternatively and comprise any suitable component disclosed herein, or is formed or be substantially made up of it by any suitable component disclosed herein.Disclosed composition can additionally or alternatively be formulated as not containing or substantially not be contained in the composition of prior art, use or to realize disclosed function and/or object not necessary any component, material, composition, auxiliary agent or kind.
In the time using word " approximately " herein, its refer to its modify amount or condition can exceed described quantitative changeization some, as long as can realize function of the present disclosure and/or object.Those skilled in the art understand not free degree of probing into any field completely, and expect that at least some extends one or more disclosed boundary to disclosed the possibility of result.Thereafter, benefiting from the disclosure and understanding under concept disclosed herein and embodiment, this area routine techniques personnel can explore and exceed disclosed boundary without creative work in the situation that, and when finding that embodiment is not when expected feature, in the implication of those embodiments in word used herein " approximately ".
Detailed Description Of The Invention
In one embodiment, described primer composition comprises liquid toughner and metal activation agent.
In one embodiment, described primer composition comprises toughner and activator and thinner.
In one embodiment, described primer composition comprises toughner and activator and reactive diluent.
In one embodiment, described primer composition comprises toughner component; And optionally comprise one or more in activator component, coactivator component, carrier component, reactive component and polymeric matrix.
Than the curable adhesive composition by identical and not containing the product of curing reaction of the primer composition of described toughner component or only form by identical curable adhesive composition bonding, the primer composition that comprises toughner component reduces and solidifies bonding fragility and improve toughness.
Can change the amount of toughner component to be applicable to concrete application.Its lower limit provides the desirable content that fragility declines and toughness improves by being to the curing reaction product of described curable compositions.Increase by the viscosity of considering cost and described primer composition the upper limit of setting toughner component.The content range of toughner component can be approximately 0.5 % by weight-Yue 50 % by weight or more of primer composition, for example, be approximately 1 % by weight-Yue 40 % by weight of primer composition, and is advantageously approximately 5 % by weight-Yue 20 % by weight of primer composition.
Some applicable toughner examples comprise elastic caoutchouc; Elastomeric polymer; Liquid elastomer; Polyester; Acrylic rubber; Butadiene/acrylonitrile rubber; Sodium butadiene rubber; Polyisobutene; Polyisoprene; Natural rubber; Synthetic rubber is as styrene/butadiene rubbers (SBR); Polyether polyols with reduced unsaturation; Ethane-acetic acid ethyenyl ester polymkeric substance; Viton; Isoprene-acrylonitrile polymer; Chlorosulfonated polyethylene; Polyvinyl acetate ester homopolymer; Segmented copolymer; Core-shell rubber grain and their mixture.The selection of described toughner component will be arranged every character and the feature of described primer composition to a great extent, and finally arranges every character and the feature of the curing reaction product of described binder composition.
The form of described toughner will depend on selected material, and can comprise particle, nano particle, have different hardness layer core-shell particles, liquid, solution and discrete phase.
Some applicable elastomeric polymer toughner can be to be characterized as fracture tensile strength to be greater than 1500psi (10342kPa), be preferably greater than 2000psi (13790kPa), and elongation at break is greater than 100%, be preferably greater than those of 200%.Described toughening polymer normally the Tg of (but not always) one of them block fragment lower than the segmented copolymer (comprising terpolymer) of-20 DEG C.
Using molar mass average value to be greater than approximately 100000 elastomerics is effectively, but expects that any molecular weight is greater than 5000 elastomerics and can realizes improvement.As general governing principle, this molecular weight is should be enough high toughness reinforcing to produce in subsequent coated and curing composition, but not high to making the described curable compositions can wire drawing (stringy) and be difficult to use.Preferably select in addition mooney viscosity (ML (1+4)) at 20-approximately between 60, and glass transition temperature is 15 DEG C or lower elastomerics.These are concrete limits and nisi, and the various elastomericss that do not fall into their scopes may be suitable for.
The optional suitable material from wide region of acrylic rubber toughner.More generally, these rubber are homopolymer of (i) alkyl acrylate; (ii) multipolymer of alkyl acrylate or vinylformic acid alcoxyl base ester and another copolymerisable monomer; (iii) the mutual multipolymer of alkyl acrylate; (iv) the mutual multipolymer of multiple vinylformic acid alcoxyl base ester; Or (v) any mixture of above (i)-(iv).Can comprise that diene, reactive Halogen unsaturated compound and other Acrylic Acid Monomers are as acrylamide with other unsaturated monomers of alkyl acrylate or alkoxy ester copolymerization.Described acrylic rubber also can comprise suitably limited amount (methyl) acrylate with acrylate or light alkene copolymerization.
Described block copolymer-toughened dose can comprise for example A-B-A segmented copolymer, wherein A block is the polymeric segment of vinylbenzene, vinyl cyanide, methyl methacrylate or the above some or all of mixture of vinylbenzene, alpha-methyl styrene, t-butyl styrene or other cycloalkylations, and B block is the elasticity fragment with low Tg, as derived from conjugated diolefine or its multipolymer as divinyl, or ethylene-propylene polymkeric substance.Commercially available example comprises the Americas purchased from Enichem Elastomers, the EUROPRENE SOL T 193A of Inc. and purchased from Kraton Polymers LLC, Houston, the Kraton SBR segmented copolymer of TX.
Polyether polyols with reduced unsaturation toughner for example can comprise purchased from as for example MILLATHANE polymkeric substance of the material of TSE Industries.
Applicable toughner can comprise for example United States Patent (USP) 3,496,250 (Czerwinski); United States Patent (USP) 3,655,825 (people such as Souder); United States Patent (USP) 3,668,274 (people such as Owens); United States Patent (USP) 3,864,426 (Salensky); United States Patent (USP) 4,440, the resilient material described in 910 (O ' Connor) and United States Patent (USP) 5,932,638 people such as () Righettini, adds its each content herein by reference.The commercially available toughner being suitable for comprises following commercially available, and commercial name HYCAR, purchased from The Lubrizol Corporation; VAMAC ethylene acrylic elastomers is as VAMAC G, VAMAC VCS, VAMAC VMX and VAMAC VCD, all purchased from DuPont; BLENDEX BTA III F, ACRYLOID KM 680, ACRYLOID KM 653, ACRYLOID KM 611 and ACRYLOID KM 330 multipolymers, all purchased from Rohm and Haas Company, BLENDEX101 multipolymer, purchased from Borg-Warner Corp., METABLEN C 223 multipolymers, purchased from M & T Chemicals, Inc., with KANE Ace-B multipolymer, purchased from Kaneka USA.
Liquid elastomer toughner can comprise as United States Patent (USP) 4,223,115 (people such as Zalucha); United States Patent (USP) 4,452,944 (Dawdy); United States Patent (USP) 4,769,419 (Dawdy); United States Patent (USP) 5,641,834 (people such as Abbey), United States Patent (USP) 5,710,235 (people such as Abbey) and United States Patent (USP)s 5, the elastomerics of the liquid olefin end-blocking described in 932,638 people such as () Righettini, adds the content of each document herein by reference.
Applicable toughner can comprise as United States Patent (USP) 6,225, and the lower molecular weight that 408 people such as () Huang are described and the combination of high molecular toughner, add literature content herein by reference.
Applicable toughner can comprise as core-shell particles.Core-shell particles has the layer of different hardness, for example, on rubber-like core, form duricrust.Endorse by thering is elasticity or rubber-like character (lower than approximately 0 DEG C, for example, lower than the glass transition temperature of approximately-30 DEG C) polymer materials forms, the shell that this core for example, is made up of non-elastomeric polymer-material (be that glass transition temperature is greater than normal temperature, be greater than thermoplasticity or the thermoset/cross-linked polymer of approximately 50 DEG C) surrounds.For example, endorse main by polyhutadiene, polyacrylic ester, polybutadiene/acrylonitrile mixture, polyvalent alcohol and/or polysiloxane or provide the raw material of any other monomer of low glass state invert point to form.Other rubbery polymer is also applicable to core, and it comprises butyl polyacrylate or silicone elastomer (as polydimethylsiloxane, particularly crosslinked polydimethylsiloxane).Described shell can be mainly by (methyl) acrylate (as methyl methacrylate) with suitable high glass transition temperature; Vi-ny l aromatic monomers (as vinylbenzene); Vinyl cyanide (as vinyl cyanide); Unsaturated acid and acid anhydrides (as vinylformic acid); The raw material of (methyl) acrylamide etc. forms.
Described core-shell particles can for example, by forming more than two-layer that (centronucleus of a kind of rubber-like material can be surrounded by the second core of different rubber-like material, or rubber-like endorses two shells that formed by difference and surround, or rubber grain can have the structure of soft core, duricrust, soft shell, duricrust).In one embodiment, the core-shell particles using is had by core and at least two that different chemical forms and/or the concentric shells of character forms.Described core or described shell or described core and shell can be that (as ion or covalency) is crosslinked.Described shell can be grafted on described core.The polymkeric substance that comprises shell can have one or more dissimilar functional groups (as epoxy group(ing)), described functional group can with other components of described primer composition or with other component interactions of curable compositions.
For example, endorse main by polyhutadiene, polyacrylic ester, polybutadiene/acrylonitrile mixture, polyvalent alcohol and/or polysiloxane or provide the raw material of any other monomer of low glass state invert point to form.Shell can be mainly by polymethylmethacrylate, polystyrene or polyvinyl chloride or provide the raw material of any other monomer of higher glass transition temperature to form.
Conventionally, core accounts for approximately 50 % by weight-Yue 95 % by weight of core-shell particles, and shell accounts for approximately 5 % by weight-Yue 50 % by weight of core-shell particles.
Conventionally, core-shell particles is Nano grade size.The size distribution of core-shell particles can be the particle diameter of at least 90% particle in the scope of the about 1000nm of about 3nm-, and the particle diameter of the particle that advantageously its size distribution is at least 90% is in the scope of 3nm-500nm.The mean diameter of core-shell particles is less than about 500nm, as is less than about 200nm, ideally in the scope of 25-100nm.
The method of preparing core-shell particles is well known in the art, and is described in for example United States Patent (USP) 4,419,496; 4,778,851; 5,981,659; 6,111,015; 6,147,142; With 6,180, in 693, by reference the full content of each patent is added herein.Core-shell particles is commercially available.Some commercially available core-shell particles comprise purchased from the CLEARSTRENGHT of Arkema Inc. and DURASTRENGTH particle; Purchased from KM330 and the KM323B of Rohm and Haas, full acrylic acid copolymer composition granule; Purchased from the Kureha Paraloid EXL-2655 particle that comprises divinyl-alkyl methacrylate-styrol copolymer of Kureha Chemical Industry Co.; Purchased from the Staphyloid AC-3355 that comprises acrylate-alkylmethacrylate polymer and the TR-2122 particle of Takeda Chemicals Industry Co.; Purchased from the Paraloid EXL series particle of Rohm & Haas Co..
Core-shell particles can be prepared as particle and be dispersed in the masterbatch in matrix.The method of preparing this masterbatch is described in greater detail in United States Patent (USP) 4,778,851 and United States Patent (USP) disclose in 2007/0027233, by reference the full content of each patent is added herein.Conventionally, the aqueous mixture that comprises core-shell particles can be contacted with the organic medium that is partially soluble in water, then with there is more water miscible another organic medium of lower part than the first organic medium and contact with Separation of Water and the dispersion of rubber grain in the second organic medium is provided.Then this dispersion also can be mixed as epoxy resin with required matrix, and is waited and removed volatile matter and obtain masterbatch by distillation.The masterbatch dispersion of core-shell particles in epoxy resin-base is commercially available.The masterbatch of some commercially available core-shell particles comprises purchased from the MX series of Kaneka USA with purchased from Wacker Chemie GmbH, the GENIOPERL of Germany.
Described primer composition comprises activator component conventionally.Think that activator component causes and the curing reaction of curable compositions independently, and accelerate the solidification rate of the reaction product of described primer composition and curable compositions.
Can use any activator component, as long as described activator component shows and the reactivity of required curable compositions.Curing speed by described curable compositions can be determined reactivity.If curing speed is than the curing speed containing the identical curable compositions of described activator component is not faster under the existence of described activator component, described activator component shows reactivity and can be used as activator composition.
For example, under the situation of (methyl) acrylate composition of anaerobism condition curable, described primer compound can comprise the compound containing transition metal.Described transition metal is those metals in " d " subgrade with valence electron.Such comprises IB, IIIA, IIIB, IVA, VA, VI, VII, VIIIA family metal in the periodic table of elements.Favourable transition metal comprises copper, chromium, manganese, iron, cobalt, nickel and molybdenum.Preferred transition metal is copper.The oxidation state of described transition metal is crucial especially, but preferably existence can be oxidized sometimes compared with low-oxidation-state.
Described transistion metal compound can mineral compound or the form of organometallic compound, and it comprises oxide compound, salt and organic metal chelate complex and complex compound.Suitable inorganic metal salt comprises carbonate, vitriol, nitrate, muriate, bromide, phosphoric acid salt and sulfide.Suitable organic salt comprises that alkoxide comprises acetate, hexanoate, octylate, ethyl hexyl hydrochlorate and naphthenate as methylate and ethylate and carboxylate salt.Other suitable transition metal complexes comprise acetyl pyruvate and hexafluoroacetylacetone hydrochlorate.Some applicable transistion metal compounds comprise 2 ethyl hexanoic acid copper, venus crystals, copper carbonate, copper naphthenate, cupric octoate, caproic acid copper, cupric methyl ethyl diketone and hexafluoroacetylacetone acid copper.
Described transistion metal compound can be solid or solution.Can use described in any solubilized transistion metal compound or keep the solvent of described transistion metal compound in solution, as long as described solvent and other primer components are miscible; The character of not remarkably influenced primer mixture; And as long as described solvent is easy to evaporation.Comprise alcohol, ketone and carboxylic acid for the suitable solvent that dissolves described transistion metal compound, but can find the organic solvent that other are suitable.Preferably, transistion metal compound described in the dissolution with solvents of use minimum.Use a certain amount of transition metal that obtains desired concn in primer composition containing described transistion metal compound.Preferably, be approximately 5 % by weight that are not more than total primer composition containing the amount of solution of described transistion metal compound.
The preferred solvent that can be used for dissolving described transistion metal compound is 2 ethyl hexanoic acid.The 2 ethyl hexanoic acid solution that even more preferably uses the transition metal salt that comprises 2 ethyl hexanoic acid is most preferably the 2 ethyl hexanoic acid copper in 2 ethyl hexanoic acid.2 ethyl hexanoic acid copper can be by reacting 2 ethyl hexanoic acid to be prepared with copper carbonate.Normal condition is included at approximately 90 DEG C, in the 2 ethyl hexanoic acid of 3 times of molar excess and heats copper carbonate approximately 2 hours.
The concentration of the transition metal (being different from described transistion metal compound) in described primer composition can be to provide any concentration with the required reaction level of described anaerobism tackiness agent.Conventionally, the gross weight of the concentration of described transition metal based on above-mentioned primer composition is about 0.005-approximately 0.5 % by weight, is preferably about 0.01-approximately 0.25 % by weight, and most preferably is the scope of about 0.03-approximately 0.10 % by weight.
Amine activator can be used in described primer composition.Suitable amine includes but not limited to amine reductive agent, by formula RNH 2represent primary amine, by formula R 2the secondary amine that NH represents and by formula R 3the tertiary amine that N represents, wherein each R is independently from each other alkyl, aryl, alkaryl or aralkyl, is preferably C 1-10alkyl, C 6-10aryl, C 7-15alkaryl and C 7-15aralkyl.The limiting examples of suitable amine coactivator comprises tri-n-butylamine, dimethyl-p-toluidine, dimethyl Ortho Toluidine, diethyl-p-tlouidine, 3,5-diethyl-1,2-dihydro-1-phenyl propyl pyridine (PDHP) and two-2-hydroxyethyl-para-totuidine.A kind of applicable amine is tri-n-butylamine.Other activator comprises amides or acid imide (as saccharin).
If use, described amine activator exists with volume of activation, shows and the reactive concentration of required curable compositions.Conventionally, the scope of the amine activation dosage in described primer composition is about 0-approximately 5 % by weight, and is preferably about 0-approximately 1 % by weight.Should notice that described amine activator can free form be combined existence with any other molecule, or be for example combined and be present in described primer composition with described transition metal with form complexed alternatively.
Can use other activators that are applicable to selected monomer and/or curable compositions as peralcohol, free radical promotor, radical initiator etc.
Be applicable to the peroxygen activator that anaerobism solidifies in the primer composition of use and comprise hydroperoxidation polymerization retarder, and most preferably be the organic hydroperoxide inhibitor with formula ROOH, wherein R is generally and comprises the alkyl of approximately 18 carbon at the most, is preferably and comprises alkyl, the aryl or aralkyl of approximately 12 carbon atoms at the most.The representative instance of these hydroperoxide comprises cumene hydroperoxide, methyl ethyl ketone hydroperoxide and the hydroperoxide that form as the oxygenation of methyl butene, n-Hexadecane and hexanaphthene by various other hydrocarbon.Also can adopt other peroxygen activators as hydrogen peroxide or as the material of organo-peroxide or peresters, its hydrolyzable or decomposition and form hydroperoxide.
The peroxygen activator being generally used in anaerobism composition accounts for approximately 20 % by weight that are less than of described composition conventionally, but ideally, uses them with the lower level of for example 0.1 % by weight-Yue 10 % by weight of whole compositions.
Can use the mixture of activator, as long as select them to avoid premature reaction or to solidify.
Described reactive component is the material that interacts to provide curable reaction product with curable adhesive composition.The material category that is applicable to reactive component is an acrylate, (methyl) acrylate of for example multifunctional or simple function.(methyl) acrylate comprises acrylate and methacrylic ester.Some (methyl) acrylate that are suitable for have formula CH 2=C (R) COOR 1, wherein R is H, CH 3, C 2h 5or halogen is as Cl, and R 1c 1-8monocycle-or bicyclic alkyl, in heterocycle, be up to two Sauerstoffatoms 3-8 unit heterocyclic radical, H, alkyl, hydroxyalkyl or aminoalkyl group wherein moieties be C 1-8straight chain or cladodification carbon atom chain.
Some exemplary simple function polymerizable acrylate monomers comprise Rocryl 410, HEMA, methyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, the amino propyl ester of methacrylic acid 2-and corresponding acrylate.Some exemplary polyfunctional monomers comprise PEGDMA-400 and dipropyleneglycol dimethacrylate.
Other applicable acrylate materials comprise those that fall into following structure:
Wherein R 2can be selected from the alkyl of approximately 4 carbon atoms of hydrogen, 1-, the hydroxyalkyl of approximately 4 carbon atoms of 1-, or
R 3can be selected from alkyl and the C of approximately 4 carbon atoms of hydrogen, halogen and 1- 1-8in monocycle or bicyclic alkyl, ring, be up to the 3-8 unit heterocyclic radical of 2 Sauerstoffatoms;
R 4can be selected from hydrogen, hydroxyl, and
M is equal to or greater than 1 integer, for example 1-approximately 8 or larger, for example 1-approximately 4.
N is equal to or greater than 1 integer, for example 1-approximately 20 or larger; And
V is 0 or 1.
Other applicable acrylate materials are to be selected from those of urethane acrylate that fall into following general formula:
(CH 2＝CR 5·CO·O·R 6·O·CO·NH) 2R 7
Wherein R 5h, CH 3, C 2h 5or such as Cl of halogen; R 6(i) C 1-8hydroxy alkylidene or amino alkylidenyl, (ii) optionally by C 1-3alkyl, C 1-3alkylamino, two-C 1-3the C that alkylamino replaces 1-6alkylamino-C 1-8alkylidene group, hydroxyl phenylene, amino phenylene, hydroxyl naphthylidene or amino naphthylidene; And R 7optionally by 1-4 halogen atom or by 1-3 amino or single-or two-C 1-3alkylamino or C 1-3the C that alkoxyl group replaces 2-20alkylidene group, alkenylene or cycloalkylidene, C 6-40arylidene, alkyl arylene, aryl arylidene, alkoxyl group alkylidene group or aryloxy arylidene; Or fall into the acrylate of following general formula.
(CH 2＝CR 5·CO·O·R 6·O·CO·NH·R 7·NH·CO·X-) nR 8
Wherein R 5, R 6and R 7as above definition; R 8to there is respectively at least n primary amine or the polyamine of secondary amine or hydroxyl or the non-functionality residue of polyvalent alcohol; X is O or NR 9, wherein R 9h or C 1-7alkyl; And n is the integer of 2-20.
Other applicable acrylate can be selected from the classification of acrylate, methacrylic ester and the glycidyl methacrylate of dihydroxyphenyl propane.It is the dihydroxyphenyl propane-dimethacrylate (" EBIPMA ") of ethoxylation particularly suitable.
Other applicable acrylate comprise exemplary but nonrestrictive following material: dimethacrylate two-, three-and four-glycol ester, dipropyleneglycol dimethacrylate, PEGDMA-400, dimethacrylate two (pentamethylene glycol) ester, diacrylate TEG ester, two (chloracrylic acid) TEG ester, diacrylate two glyceryl ester, tetramethyl-vinylformic acid two glyceryl ester, dimethacrylate four methylene esters, dimethacrylate ethyl, diacrylic acid pentyl diol ester, trimethyol propane triacrylate.
Can use mixture or the multipolymer of above-mentioned reactive component arbitrarily.
Described reactive component need to be with pure substance state, but can comprise and wherein comprise inhibitor or stablizer as the commodity rank of polyphenol, quinone etc.These materials as free radical inhibitors to avoid the premature polymerization of described reactive component.What be selected from by use that one or more monomers in above those or other for example unsaturated monomer of additive (comprising unsaturated hydrocarbons and unsaturated ester) of enumerating obtain curing composition improves character also in the scope of the present disclosure.
The amount of described reactive component can be approximately 50 % by weight-Yue 90 % by weight of described primer composition, for example, be approximately 60 % by weight-Yue 80 % by weight of described primer composition.
Can optionally use carrier component to reduce the viscosity of described primer component.More low viscous like this primer composition can be advantageously used in the core sucting action between the adhesive surface of tight spacing, has little cured body between the gap between described surface.If exist, described carrier preferably can load described in primer composition to the liquid of adhesive surface, and within the desirable short period of time, volatilize subsequently.
Described carrier should have multinomial favourable character.The first, under about normal pressure, and it should be liquid under the temperature range of approximately 15 DEG C of (59 °F)-Yue 35 DEG C (95 °F).The second, described carrier should be non-flammable, that is to say that described compound does not show flash-point under the arbitrary temp that is not more than approximately 93 DEG C (200 °F).Such carrier also can be called as nonflammable, because the flammable compound of definition shows as the flash-point less than or equal to 38 DEG C of (100 °F) temperature.The 3rd, described carrier should be not destroy ozone, and this refers to that it is zero substantially that described compound demonstrates the destruction possibility of ozone.
Some applicable carriers comprise with lower one or more: water; Lower paraffin hydrocarbons is as pentane, hexane, heptane; Lower alcohol is as methyl alcohol, ethanol, Virahol; Lower ketones is as acetone; Halogenated compound; Glycol ethers is as n-butoxy propyl alcohol, propylene glycol monomethyl ether and 2-butoxy-1-propyl alcohol; More low viscous reactive monomer.Also applicatory is as United States Patent (USP) 5,811, the azeotropic combination of disclosed carrier in 473.The amount of described carrier is enough to dissolve or disperse other component.The amount of common described carrier is approximately 10 % by weight-Yue 90 % by weight of described primer composition.
Described primer composition is optionally made illiquidity, be that they can be at least 70 °F (21 DEG C), preferably be no more than approximately 120 °F (49 DEG C), and be advantageously no more than at the temperature at least about 160 °F (71 DEG C) and exist and do not move with the agglomerate of self-supporting.Such illiquidity primer composition can be advantageously used in and be bonded in the assembly between adhesive surface with large space, and therefore between gap, has large cured body.Illiquidity primer composition comprises polymeric matrix.Described polymeric matrix comprises that common fusing point or softening point range are at approximately 200 °F of (93 DEG C)-Yue 500 °F (260 DEG C), more preferably greater than the organic materials of 250 °F of (121 DEG C)-Yue 500 °F (260 DEG C).At United States Patent (USP) 7,408, polymeric matrix is described in 010, by reference its full content is incorporated herein.In the present invention, applicable polymer materials can be selected from the aliphatic hydrocrbon (as the rheologic additive based on Viscotrol C) of urea-carbamate, hydroxyl or amine modification, rheologic additive based on liquid polyester-acid amides and their composition.That fusing point is the polyamide material of approximately 260 °F (127 DEG C) particularly suitable.
Described polymeric matrix can described composition gross weight approximately 2.0 % by weight-Yue 20 % by weight, for example approximately 5 % by weight-Yue 15 % by weight, the amount of 7 % by weight according to appointment-Yue 10 % by weight exists.In the time existing with this tittle, can obtain the illiquidity character of composition, and undesired effect (for example cured product intensity or sealed with cured product loss of energy) minimum.
In primer composition, advantageously use as known in the art for giving inhibitor and the sequestrant of polymerisable compound stability.Those inhibitor that are applicable to the present composition are selected from any known inhibitor, and it comprises and is selected from quinhydrones, benzoquinones, naphthoquinones, phenanthrenequione, anthraquinone and those of substitution compound arbitrarily in these.In sequestrant, can optionally be present in described binder composition is beta-diketon, ethylenediamine tetraacetic acid (EDTA) (" EDTA ") and EDETATE SODIUM salt.Described inhibitor and sequestrant can be respectively with the content uses of 0.1 % by weight-Yue 1 % by weight according to appointment.
In thickening material, fluidizer, linking agent, pigment, dyestuff, thinner, filler and other binder formulations known reagent can any reasonable manner for the preparation of known functional property, as long as they not obviously deteriorated primer composition make bonding toughness reinforcing character.With respect to conventional thread locking system, the amount that inert filler can be relatively high exists.Increase the oilness of composition and the weighting agent of stopping property as TEFLON (tetrafluoroethylene) and polyethylene may be favourable in some applications.
Described primer composition can be by adding respectively each component of described composition and fully mixing and prepare with any order.Advantageously before adding polymer matrix material, add inhibitor and sequestrant.Common described primer composition is basic mixture uniformly.In one embodiment, transistion metal compound solid or in solution is dissolved at least part of alkanol, and by gained solution for the preparation of described composition.Toughner component dissolves in described carrier or other components, and can be by gained mixture for the preparation of described composition.If use, can add amine coactivator in any step.Stir with other stirring form and be generally used for helping this mixing process.This mixing is carried out conventionally under normal pressure and temperature, but the applicable temperature of approximately 35 DEG C at the most.Conventionally, need in preparation process, transistion metal compound or the relative oxygen of coactivator amine not protected.In another embodiment, under mixing, toughner component is added in reactive component.Can add body material and form illiquidity primer composition.Can not need in this embodiment solvent and carrier.
In one embodiment, can comprise through toughness reinforcing primer composition:
Described primer composition is applied on surface to be bonded.Can be using before described curable adhesive composition, simultaneously or afterwards described primer composition is applied on adhesive surface.Described primer composition can be applied on surface to be bonded by any ordinary method.For the primer composition of liquid form, adhesive surface can be immersed in the container that comprises described primer composition, or use described primer composition spraying, or use described primer composition obliterating or brushing.For the primer composition of liquid form not, can use the friction of primer composition rod or " delineating " described adhesive surface.The limiting examples of adhesive surface material comprises that metal is as surface and the stainless steel of aluminium, copper, magnesium, steel, zinc-plated and cadmium plating.After being applied to adhesive surface, if exist, carrier component being evaporated and other components are stayed on treated adhesive surface.Be approximately 30 seconds～approximately 5 minutes common aerial time of drying.Remaining primer composition is stable, and can stay on treated adhesive surface and reach approximately 30 days or more of a specified duration, and does not affect the interactional ability of itself and curable compositions.Primer composition and curable compositions are not interchangeable.Be different from curable compositions, primer composition can self not solidify.Primer composition must interact to make described primer composition to start to solidify with curable compositions.
Primer can be used in advance, for example, before surface contacts with another adhesive surface, be applied on this surface, or can use later, for example, be applied on the adhesive surface having contacted.
In one embodiment, primer composition is applied on first surface to be bonded.Binder composition is applied on the second surface to first surface to be bonded.Second surface is contacted with first surface.Accelerate solidifying of described curable compositions by described activator component.
In one embodiment, primer composition is applied on first surface to be bonded.Then binder composition is applied on the first adhesive surface subsequently on described primer composition.Second surface is contacted with described first surface.
In one embodiment, primer composition and binder composition are applied on first surface to be bonded simultaneously.Can respectively described primer composition and described binder composition be applied on the first adhesive surface or can for example be mixed by mixing nozzle, and mixture is applied on the first adhesive surface.Second surface is contacted with described first surface.
In one embodiment, surface to be bonded is in contact with one another and is limited interface or the glue-line between the adhesive surface contacting.Primer composition and the optional binder composition existing are applied to the interface between surface in contact.Conventionally described primer composition adjacent interface is used, and described primer composition has the low viscosity that is suitable for wicking into the interface between surface in contact.
With respect to the curable compositions that does not use described primer composition, of the present invention through toughness reinforcing primer composition be applicable to and curable compositions together with use to provide required toughness reinforcing bonding between base material.Described primer composition is effectively for making bonding toughness reinforcing between metal and metal base, and believes that for making bonding toughness reinforcing between plastic basis material and metal or plastic basis material be effective.
In a favourable embodiment, first surface is the moon end connection section of high pressure web member, and second surface is the complementary oedoeagus connection section of this high pressure web member.Oedoeagus connection section can be fixed in cloudy end connection section and form high pressure web member.High pressure web member is applicable in gas compression system and cooling system, for example, transport HVAC system in refrigerator, refrigerator, refrigerator-refrigerator, air-conditioning, heat pump, house heating, ventilation and artificial atmosphere (" HVAC ") system, business HVAC system or for example automobile, truck, train, aircraft or ship.In the U. S. application 12/358,798 of submitting on January 23rd, 2009, describe high pressure web member in detail, its content is all quoted and is incorporated to herein.In an embodiment of using in advance, described primer composition is applied on the surface of one of described end connection section.Curable adhesive composition is applied on end connection section surface.Described tackiness agent can be applied on the end connection section surface identical with described primer composition, or is applied on complementary end connection section surface.Oedoeagus connection section is inserted to cloudy end connection section and will hold the part that connection section is bonding and be sealed, and form high pressure web member.Can advantageously rotate during insertion oedoeagus part so that described primer composition and binder ingredients contact maximization.The end connection section of assembling can be kept together the several seconds to several minutes with make bonding two end connection sections adhesive portion solidify.
In the embodiment of using after, described oedoeagus connection section is inserted in described cloudy end connection section.Described primer is applied to the end connection section that contacts wicking to therebetween.Before assembling end connection section applied adhesives composition, with described primer composition simultaneously applied adhesives composition or after using described primer composition applied adhesives composition.This assembly can be kept together the several seconds to several minutes with make bonding two end connection sections adhesive portion solidify.
The amount that is applied to the primer composition on adhesive surface should provide film, and is conventionally no more than effective quickening bonding operation and the necessary degree of required increasing tougheness of reaching.Excessive primer composition can affect final bonding intensity.For most of objects, gratifying usage rate scope be 1 part of primer composition to 1 part of curable compositions (1: 1) to 1 part of primer composition to 10 parts of curable compositions (1: 10).
Described primer composition can be advantageously uses together with can anaerobism curing acrylate or methacrylate adhesives composition.The exemplary curable adhesive composition that intention is used together with primer composition disclosed herein comprises (methyl) Acrylic Acid Monomer that is conventionally mixed with peroxide initiator.These composition remain stables, and not solidifying under air (oxygen) exists, but polymerization and form hard, durable reaction product in the time removing air or oxygen.This curable compositions is particularly suitable as bonding for bonding metal and other non-porous or non-ventilative materials of tackiness agent.Useful especially as adhesive material is polymerisable propylene dimer acid esters and other polyacrylic ester.The limiting examples of suitable mono acrylic ester monomer comprises Propenoic acid, 2-methyl, isobutyl ester, vinylformic acid cyano group ethyl ester, methacrylic acid hydroxyl ethyl ester, methacrylic acid hydroxyl propyl ester and cyclohexyl acrylate.The limiting examples of suitable polymerisable polyacrylic ester comprise dimethacrylate two-, three-and four-glycol ester, dipropyleneglycol dimethacrylate, PEGDMA-400 and ethoxylation bisphenol a dimethacrylate.Applicable acrylate also comprises those that form that react of acrylate by comprise active hydrogen atom in the alcohol moiety of ester and organic isocyanate.The acrylate that these and other are suitable, comprises that the formulation of urethane acrylate etc. and they and organo-peroxide polymerization initiator, stablizer and properties-correcting agent is described in greater detail in following United States Patent (USP) 3,591,438; United States Patent (USP) 3,218,305; United States Patent (USP) 4,018,851; United States Patent (USP) 3,993,815; United States Patent (USP) 3,925,988; With United States Patent (USP) 4,309, in 526, its relevant portion is quoted and is incorporated to herein.The binder composition of commercially available anaerobically curable is extensively available, for example with trade mark LOCTITE purchased from Henkel Corporation of Rocky Hill Connecticut.
Following examples illustrate the each side of the present composition, comprise preparation method and the purposes of described composition.Except as otherwise noted, all per-cents in embodiment are based on weight percent.
Following examples are for the object that illustrates to make the disclosure can be easier to understand, and its intention is never restriction the scope of the present disclosure, unless separately had specifically and indicated.
Embodiment
Multiple copper pipes and aluminum pipe are provided.Each pipe fitting is nominal 5/16 inch diameter.Each pipe fitting at one end has sun or cloudy end.In the time that oedoeagus portion inserts cloudy end, described end can obtain the radius clearance of the overlapping and 0.002-0.006 inch of the length of approximately 3/4 inch.
Select a pair of pipe fitting, one has oedoeagus portion, and another root has cloudy end.This can be all copper pipe, all be that aluminum pipe or one are that copper pipe and one are the combinations of aluminum pipe pipe fitting.If suitable, clean surface to be bonded with Virahol.By binder composition applied as thin films to oedoeagus connection section, and if use, by primer composition with applied as thin films Zhiyin end connection section.Oedoeagus connection section is inserted to cloudy end connection section, and between end, do not rotate and obtain 3/4 inch overlapping, and original position keeps approximately 30 seconds.After 30 seconds, described tackiness agent and primer are cured to be enough to keeping pipe fitting location without auxiliary in the situation that.Before carrying out seepage test, can make bonding assembly at the lower curing certain hour of room temperature (RT).Each seepage test used new bonding assembly.
Original pressure test:
Bonding assembly is at room temperature solidified to about 2-approximately 10 minutes.Use the pressure of helium to curing assembly internal pressurization to about 400psi.To be immersed in the water through the assembly of pressurization.Spill helium bubbles from adhesion area and count failure.Test routinely 3 assemblies.
High (UL 250) pressure test:
Bonding assembly is at room temperature solidified approximately 2 hours.Curing assembly inside is placed under the pressure that uses oily 2000psi, and any seepage is counted to failure.Test routinely 3 assemblies.
Burst pressure test:
Bonding assembly is at room temperature solidified approximately 72 hours.Curing assembly inside is placed under the pressure of continuous rising, and any seepage is counted to failure.Test routinely 3 assemblies.
Thermal cycling test:
Bonding assembly is at room temperature solidified 24 hours.Curing assembly is exposed to and in following temperature cycle, is carried out in 500 circulations: under-10 °F, keep 1 hour, heating, from-10 °F to 275 °F, keeps 1 hour under 275 °F in 1 hour, cooling from 275 °F to-10 °F in 1 hour.After completing 500 circulations, bonding assembly is returned to room temperature.Bonding assembly under room temperature is placed under the pressure that uses oily 2000psi (UL 250 tests), and any seepage is counted to failure.Test routinely 3 assemblies.Can be by the Enviroflex of Envirotronics 300 series of tests instrument for this thermal cycling test.
Thermal shock test:
Bonding assembly is at room temperature solidified 24 hours.Curing assembly is exposed to and in following temperature cycle, carries out 500 circulations: in 0 °F of refrigerant, place 5 minutes, in 300 °F of baking ovens, place 5 minutes, in 0 °F of refrigerant, place 5 minutes.After completing 500 circulations, bonding assembly is returned to room temperature.Bonding assembly under room temperature is placed under the pressure that uses oily 2000psi (UL 250 tests), and any seepage is counted to failure.Test routinely 3 assemblies.Can be by Blue M Pro Star type WSP1098MP3 test box for this thermal shock test.
Vibration test:
Bonding assembly is at room temperature solidified 24 hours.Curing assembly is placed in the container (beaker) that is fixed on vibration mixing platform.Make this bonding assembly free movement in container.Set mixing platform and carry out the motion of 3/8 inch; 300 motions/minute.Test continues 200 hours.Complete after test in 200 hours, bonding assembly is placed under the pressure that uses oily 2000psi (UL 250 tests), and any seepage is counted to failure.Test routinely 3 assemblies.
Refrigeration agent compatibility test (NEMA RE2):
Bonding assembly is at room temperature solidified 24 hours.A kind of in use test refrigeration agent by curing assembly internal pressurization to 400psi.Described test refrigeration agent is R134A; The polyol ester refrigeration oil of R134A and standard; R410A; And the polyol ester of R410A and standard refrigeration oil.After completing the test of 240 hours, bonding assembly is placed on (UL250 test) under the 2000psi pressure that makes water, and records any seepage.Failure under any test refrigeration agent is considered as the failure of refrigeration agent compatibility test.Test routinely 3 assemblies.
Embodiment 1: use following material.All per-cent is based on weight.Tackiness agent for bonding all pipe fittings is LOCTITE 640.LOCTITE 640 is described as the single component high strength acrylic acid tackiness agent curing by anaerobism mechanism by technical data sheet.Technical data sheet is described as LOCTITE 7387 in the low viscosity activator that promotes that acryloid cement is curing.Having indicated LOCTITE 7387 comprises solvent but does not indicate and comprise reactive component.LOCTITE 7088 is described as solvent-free, the wax-like semi-solid primer for an aerobic curing binder by technical data sheet.Indicate LOCTITE 7088 and comprised dimethacrylate reactwity of monomer component, and indicated it and there is anaerobism curing mechanism.3 kinds of differing materials are mixed respectively to primer composition A, the B and the C that provide toughness reinforcing with LOCTITE 7088.25% the mixture of core/shell particle in 75% epoxy resin and the LOCTITE 7088 of 90 % by weight that composition A comprises 10 % by weight, described mixture with trade(brand)name MX125 purchased from Kaneka USA.The LOCTITE 7088 of styrene-butadiene-styrene block copolymer particle that composition B comprises 10 % by weight (with trade(brand)name KRATON D1155ES purchased from Kraton Polymers LLC, Houston TX) and 90 % by weight.The LOCTITE 7088 of the liquid state that composition C comprises 10 % by weight, the polybutadiene of maleinization (with trade(brand)name RICON 131MA10 purchased from Sartomer Company, Inc., Exton PA) and 90% % by weight.
In following table 1, gather test result.
---represent not test.
1lOCTITE 640, purchased from Henkel Corporation, Rocky Hill, Connecticut.
2lOCTITE 7387, purchased from Henkel Corporation, Rocky Hill, Connecticut.
3lOCTITE 7088, purchased from Henkel Corporation, Rocky Hill, Connecticut.
4a is the Kaneka MX125 of 10 % by weight and the LOCTITE 7088 of 90 % by weight.
5b is the Kraton D1155ES of 10 % by weight and the LOCTITE 7088 of 90 % by weight.
6c is the Sartomer RICON 131MA10 of 10 % by weight and the LOCTITE7088 of 90 % by weight
As shown in by the result of table 1, only use the bonding assembly of LOCTITE 640 tackiness agents both not test also not by UL 250 pressure tests by original pressure.A part is used LOCTITE640 another part to use the bonding assembly of LOCTITE 7387 to pass through original pressure test, but not by UL 250 pressure tests.A part is used LOCTITE 640 another part to use the bonding assembly of LOCTITE 7088 to pass through original pressure test and UL 250 pressure tests.These assemblies have also passed through vibration test and refrigeration agent compatibility test.These assemblies are not by thermal cycling or thermal shock test.A part is used LOCTITE 640 and toughness reinforcing primer composition A, B and the bonding assembly of C to pass through all tests.This test result shows that the bonding toughness reinforcing primer composition that can the application of the invention of the tackiness agent between metal base carries out toughness reinforcing.
Embodiment 2: all per-cent is based on weight.Tackiness agent for bonding all pipe fittings is LOCTITE 640.The main ingredient of composition D is as follows:
1KRATON?D1155ES
Exist other components of composition D to increase painted or change and toughness reinforcing incoherent other character.
Select aluminium or copper pipe, and by preparation as mentioned above.Tackiness agent is applied to oedoeagus, and primer composition D is used to Zhiyin end.Pipe fitting is connected, overlapping approximately 0.75 inch, erect and place 72 hours and test.Use the pinblock speed of 0.2in/min, test tensile strength on Instron tester for elongation.In following table 2, gather test result.
1lOCTITE 640, purchased from Henkel Corporation, Rocky Hill, Connecticut.
As shown in the result in table 2, use LOCTITE 640 tackiness agents and the toughness reinforcing bonding assembly of primer composition D to pass through initial testing and spalling test, and be applicable to form high pressure web member.This test result demonstrates the bonding toughness reinforcing primer composition that can the application of the invention of tackiness agent between metal base and carries out toughness reinforcing.It is bonding applicable to bonding parts or assembly except fluid web member that the tensile strength showing in table 2 shows to use tackiness agent and increasing tougheness primer composition to obtain.
Although provided for purposes of illustration preferred embodiment, above explanation should not be considered as restriction disclosed herein.Therefore, those skilled in the art can expect various amendments, change and replacement, and do not deviate from spirit and scope of the present disclosure.

Claims (18)

1. primer composition, it is by toughner component; Copper activator component, chromium activator component, manganese activator component, iron activator component, cobalt activator component, nickel activator component or molybdenum activator component; Form with reactive component;
Described toughner component is segmented copolymer;
Described reactive component is (methyl) acrylate.
2. primer composition according to claim 1, it further comprises amine coactivator component and/or carrier component.
3. primer composition according to claim 2, wherein said amine coactivator component is selected from tri-n-butylamine, dimethyl-p-toluidine, dimethyl Ortho Toluidine, diethyl-p-tlouidine, 3,5-diethyl-1,2-dihydro-1-phenyl propyl pyridine and two-2-hydroxyethyl-para-totuidine.
4. primer composition according to claim 1, wherein activator component is copper compound.
5. primer composition according to claim 1, it also comprises the polymeric matrix of 2 % by weight-20 % by weight, and wherein said primer composition is illiquidity.
6. primer composition according to claim 1, it has liquid form.
7. primer composition according to claim 1, wherein said reactive component is simple function (methyl) acrylate or polyfunctional (methyl) acrylate.
8. primer composition according to claim 1, wherein said reactive component is selected from acrylate, the methacrylic ester of dihydroxyphenyl propane and the glycidyl methacrylate of dihydroxyphenyl propane of urethane acrylate, dihydroxyphenyl propane.
9. make the bonding toughness reinforcing method of tackiness agent, it comprises:
First surface to be bonded is provided;
Primer composition claimed in claim 1 is coated on described first surface;
Described toughner component is contacted with curable adhesive composition;
Described binder composition is exposed to and is suitable for solidifying under the condition of described binder composition, and it is bonding that the reaction product that makes to have solidified forms toughness reinforcing tackiness agent,
The bonding ratio of wherein said toughness reinforcing tackiness agent be not coated with by solidify described curable compositions on described surface tackiness agent that described primer composition forms bonding be more difficult for crisp.
10. method according to claim 9, wherein said primer composition is as extremely described first surface of liquid application.
11. methods according to claim 9, are wherein applied to second surface to be bonded by described curable adhesive composition, and the second surface of using curable adhesive composition is contacted with the described first surface of using primer composition.
12. methods according to claim 9, wherein said primer composition and described curable compositions are all applied on first surface to be bonded, and second surface is contacted with described first surface.
13. methods according to claim 9, wherein align first surface to be bonded and between first surface and second surface, form interface with second surfaces to be bonded, and described primer composition is applied to described interface.
14. methods according to claim 9, one of wherein said surface is plastics.
15. prepare the method for high pressure web member, and described web member is mainly made up of the product of curing reaction of the composition of the first pipe fitting, the second pipe fitting and free-radical curable, and described method comprises:
First pipe fitting with end connection section is provided;
Second pipe fitting with end connection section is provided;
Primer composition claimed in claim 1 is applied on one of described end connection section;
Curable compositions is applied on one of described end connection section;
The end connection section that the end connection section of the second pipe fitting is slipped into the first pipe fitting, the outside surface of the first pipe fitting is determined the outside surface of described high pressure web member, and the internal surface of the second pipe fitting is determined the internal surface of described high pressure web member; With
Described curable compositions is solidified so that the end connection section of the second pipe fitting remains in the end connection section of the first pipe fitting, form thus described high pressure web member.
16. methods according to claim 15, are wherein applied to first end connection section by described primer composition, and described curable compositions is applied to the second end connection section.
17. methods according to claim 15, are wherein applied to first end connection section by described primer composition, and described curable compositions is applied to described first end connection section.
18. methods according to claim 15, are wherein applied to described primer composition the interface between the first outer surface of pipe fittings and the second inner surface of pipe fitting.
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